Use of a catalyst in a hydrogenolysis process

ABSTRACT

A catalyst used for liquefaction of coal and hydrogenolysis or hydrodesulfurization of heavy oils. The catalyst is prepared by reacting one or more compounds selected from the group consisting of carbonyl compounds of molybdenum, salts of molybdenum, oxides of molybdenum, metallic molybdenum, and alloys containing molybdenum, with alkali and water at a temperature ranging from 220° to 450° C. under a carbon monoxide atmosphere; and reducing the product obtained at temperature ranging from 400° to 450° C. under a hydrogen atmosphere.

This application is a division of Ser. No. 500,914, filed June 3, 1983now U.S. Pat. No. 4,467,049.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a catalyst used for liquefaction ofcoal and hydrogenolysis or hydrodesulfurization of heavy oils.

2. Description of the Prior Art

Conventionally, as catalysts for hydrogenolysis or hydrodesulfurizationof heavy oils, oxides of Co-Mo, Mo-Ni or Ni-W compounds have been usedtogether with carriers such as alumina and silica. These catalysts, whenused in residual oil of heavy oil or in asphalt, have an extremelylowered catalytic activity, and are permanently poisoned, and it isalmost impossible to regenerate them.

The object of the present invention is to solve this problem and toprovide a catalyst which is high in activity, easy to regenerate, andsuited particularly to hydrogenolysis or hydrodesulfurization of heavypetroleum oils.

SUMMARY OF THE INVENTION

The catalyst conforming to the present invention is produced by causingor one or more compounds selected from the group consisting of (a)carbonyl compounds of molybdenum, (b) salts of molybdenum, (c) oxides ofmolybdenum, (d) metallic molybdenum, and (e) alloys containingmolybdenum to react with alkali and water at temperature ranging from220° to 450° C. in a carbon monoxide atmosphere, and reducing theproduct from this reaction at a temperature ranging from 400° to 450°C., together with a phenol, in a hydrogen atmosphere.

According to the present invention, it is possible to obtain a catalystwhich has a high activity, is easy to regenerate, and is suitedparticularly to liquefaction of coal and hydrogenolysis orhydrodesulfurization of heavy petroleum oils.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 are charts of differential thermal analysis;

FIGS. 3 and 4 are electron spectra by ESCA;

FIG. 5 is an X-ray diffraction chart; and

FIGS. 6 and 7 are infrared ray absorption spectra.

In the drawings P1 to P12 refer to peaks.

As the carbonyl compound of molybdenum (a), molybdenum carbonyl isappropriate. As the salts of molybdenum (b), for example, any one ofammonium salt, nitrate, chloride, carbonate and organic acid salt may beused, of which ammonium salt is most preferable. As the oxide ofmolybdenum (c), a trioxide may be preferably employed. As the alloycontaining molybdenum (e), for example, SCM, SKH, SUS containingmolybdenum by at least 0.3 weight percent may be used. A catalyst formedon an alloy is excellent in mechanical strength and is easy toregenerate. As the alkali, a carbonate or phosphate of an alkali metal,for example, sodium carbonate or, sodium phosphate, or any other similarsubstance may be used provided it is expressed by a general formula ofMOH. In this expression, M refers to an alkalin metal or ammonium group,and also to an alkaline earth metal such as calcium or barium.

To introduce a carrier into the catalyst conforming to this invention,the carrier may be mixed with the catalyst components before adding thealkali and water in the manufacturing process. As the carrier,diatomaceous earth, pumice, activated carbon, silica gel, or alumina maybe used. Besides, the catalyst conforming to this invention may beformed by melting and depositing the catalyst components on the carriersurface of a proper shape, and it is also possible to melt and depositthe catalyst components on the carrier surface inside a reactionapparatus, so that the reaction may effectively progress. Furthermore,if the activity of the catalyst conforming to the present invention islowered in the course of use, it may be regenerated by causing it toreact, after heat treatment, with alkali and water at a temperature of220° to 450° C. in a carbon monoxide atmosphere, rinsing the reactionproduct, and reducing the product together with a phenol at atemperature of 400° to 450° C. in a hydrogen atmosphere.

The following examples serve to illustrate the present invention butshould not be construed as imposing any limitations on the invention.

EXAMPLE 1

To 5 g of molybdenum carbonyl were added 15 g of sodium hydroxide and 10ml of water, and the mixture was heated for an hour at 410° C. in acarbon monoxide atmosphere (initial pressure 100 kg/cm²). The reactionproduct was thoroughly washed in warm water, and heated to dryness at100° C. under reduced pressure. To 2.6 g of this dried black reactionproduct were added 1 g of catechol as phenol and 25 ml of tetralin asmedium oil, and the mixture was allowed to react for an hour at 420° C.in a hydrogen atmosphere (hydrogen initial pressure 100 kg/cm²). Thereaction product was filtered, cleaned sufficiently in benzene, anddried at 120° C. for 24 hours under reduced pressure to give a catalyst(yield 2.51 g).

To 15 g each of heavy oil A, heavy oil B, and paving asphalt was added30.0 mg of the above catalyst, and a hydrogenolysis reaction wasconducted for an hour each at 440° C., 460° C., and 480° C. in ahydrogen atmosphere (hydrogen initial pressure 50 kg/cm²). The reactionproduct was distilled at atmospheric pressure. The result is shown inTable 1. As a control, reactions without catalyst are also shown.

                  TABLE 1                                                         ______________________________________                                                             Yield by distilling                                      Temper-              temperature (wt. %)                                             ature             Less                                                 Type of                                                                              of hydro-         than  75 to 175 to                                                                              Over                               oil    genolysis                                                                              Catalyst 75° C.                                                                       175° C.                                                                      220° C.                                                                      220° C.                     ______________________________________                                        Heavy  440° C.                                                                         Not used 0.6   11.1  16.8  72.3                               Oil A           Used     13.2  31.7  36.4  18.7                                      460° C.                                                                         Not used 3.2   23.6  21.9  67.9                                               Used     20.6  55.3  --    24.1                                      480° C.                                                                         Not used 4.8   22.9  12.1  60.2                                               Used     38.9  47.2  --    13.9                               Heavy  440° C.                                                                         Not used 4.7   11.8  24.1  56.4                               Oil B           Used     10.7  37.6  24.1  27                                        460° C.                                                                         Not used 9.5   14.0  22.7  50.8                                               Used     21.1  40.2  --    38.7                               Paving 440° C.                                                                         Not used trace trace 36.6  63.4                               asphalt         Used     6.7   26.1  14.0  52.0                                      460° C.                                                                         Not used trace 8.2   30.2  61.6                                               Used     9.5   19.1  24.8  46.6                                      480° C.                                                                         Not used 4.8   12.1  21.6  61.5                                               Used     23.6  12.0  21.7  42.7                               ______________________________________                                    

In this table, the yield refers to the percentage by weight of theproduct. A trace means less than 0.01%.

As evident from Table 1, the yield at low distilling temperature isnotably increased by using the catalyst conforming to the presentinvention as compared with the control without catalyst.

EXAMPLE 2

5 g of molybdenum oxide was mixed with 15 g of sodium hydroxide and 10ml of water, and the mixture was heated for an hour at 410° C. in acarbon monoxide atmosphere (initial pressure 100 kg/cm²). The reactionproduct was thoroughly washed in warm water, and heated to dryness at100° C. under reduced pressure. To 2.6 g of thus dried reaction productwere added 1 g of catechol as phenol and 25 ml of tetralin as mediumoil, and the mixture was allowed to react for an hour at 420° C. in ahydrogen atmosphere (hydrogen initial pressure 100 kg/cm²). The reactionproduct was filtered, cleaned sufficiently in benzene, and dried at 120°C. for 24 hours under reduced pressure to give a catalyst.

To 15 g each of heavy oil A, heavy oil B, and paving asphalt was added30.0 mg of the above catalyst as in the case of the previous example,and a hydrogenolysis reaction was conducted for an hour each at 440° C.,460° C., and 480° C. in a hydrogen atmosphere (hydrogen initial pressure50 kg/cm²). The reaction product was distilled at atmospheric pressure.The obtained result was almost the same as the data in Table 1.

EXAMPLE 3

Five sheets of stainless steel measuring 3.2 cm in length, 1.5 cm inwidth and 2 mm in thickness were manufactured from SUS316 specified inthe Japanese Industrial Standard containing molybdenum in an amount of 3to 5 wt.%, to which were added 5 g of sodium hydroxide and 10 ml ofwater, and the mixture was heated for an hour at 410° C. in a carbonmonoxide atmosphere (initial pressure 100 kg/cm²). The reaction productwas thoroughly washed in warm water, and heated to dryness at 100° C.under reduced pressure. To 2.6 g of thus dried reaction product wereadded 1 g of catechol as phenol and 25 ml of tetralin as medium oil, andthe mixture was allowed to react for an hour at 420° C. in a hydrogenatmosphere (hydrogen initial pressure 100 kg/cm²). The reaction productwas filtered, cleaned sufficiently in benzene, and dried at 120° C. for24 hours under reduced pressure to give a catalyst.

To 15 g each of heavy oil A, heavy oil B, and paving asphalt was added30.0 mg of the above catalyst as in the case of the previous examples,and a hydrogenolysis reaction was conducted for an hour each at 440° C.,460° C., 480° C. in a hydrogen atmosphere (hydrogen initial pressure 50kg/cm²). The reaction product was distilled at atmospheric pressure. Theresult is shown in Table 2. As a control, reactions without catalyst arealso shown.

                  TABLE 2                                                         ______________________________________                                                             Yield by distilling                                      Temper-              temperature (wt. %)                                             ature             Less                                                 Type of                                                                              of hydro-         than  75 to 175 to                                                                              Over                               oil    genolysis                                                                              Catalyst 75° C.                                                                       175° C.                                                                      220° C.                                                                      220° C.                     ______________________________________                                        Heavy  440° C.                                                                         Not used 0.6   11.1  15.1  73.2                               Oil A           Used     7.0   24.2  35.7  33.1                                      460° C.                                                                         Not used 3.2   15.9  14.1  67.9                                               Used     15.5  32.7  25.1  26.7                                      480° C.                                                                         Not used 4.8   22.9  12.1  60.2                                               Used     26.8  49.6  8.6   15.6                               Heavy  440° C.                                                                         Not used 0.8   12.2  24.9  62.1                               Oil B           Used     10.2  29.6  10.3  49.9                                      460° C.                                                                         Not used 3.8   14.5  23.4  52.4                                               Used     16.4  21.3  25.0  37.2                                      480° C.                                                                         Not used 7.8   22.3  16.6  43.3                                               Used     25.6  41.5  7.5   25.4                               Paving 440° C.                                                                         Not used 0     0     36.6  63.4                               asphalt         Used     3.0   10.2  27.5  59.3                                      460° C.                                                                         Not used 0     8.2   30.2  61.6                                               Used     7.4   28.0  16.0  47.6                                      480° C.                                                                         Not used 0     12.1  21.6  61.5                                               Used     12.3  35.0  --    53.7                               ______________________________________                                    

The yield refers to the percentage by weight of the product.

EXAMPLE 4

Five bars measuring 0.8 cm in diameter and 2 cm in length weremanufactured by SKH9 specified in the Japanese Industrial Standardcontaining molybdenum in an amount of 5 to 6 wt.%, to which were added 5g of sodium hydroxide and 10 ml of water, and the mixture was heated foran hour at 410° C. in a carbon monoxide atmosphere (initial pressure 100kg/cm²). The reaction product was thoroughly washed in warm water, andheated to dryness at 100° C. under reduced pressure. To 2.6 g of thusdried reaction product were added 1 g of catechol as phenol and 25 ml oftetralin as medium oil, and the mixture was allowed to react for an hourat 420° C. in a hydrogen atmosphere (hydrogen initial pressure 100kg/cm²). The reaction product was filtered, washed sufficiently withbenzene, and dried at 120° C. for 24 hours under reduced pressure togive a catalyst.

To 15 g each of heavy oil A, heavy oil B, and paving asphalt was added30.0 mg of the above catalyst as in the case of the previous examples,and a hydrogenolysis reaction was conducted for an hour each at 440° C.,460° C., and 480° C. in a hydrogen atmosphere (hydrogen initial pressure50 kg/cm²). The reaction product was distilled at atmospheric pressure.The obtained result was almost same as the data in Table 2.

In the above examples, catechol was used as phenol, but monovalentphenols or other polyvalent phenols may also be used in other examplesof the present invention.

Similarly, in the above examples, tetralin was used as medium oil, butdiphenylmethane or other medium oil may be used in the presentinvention.

The catalyst conforming to this invention is applicable not only toliquefaction of coal and hydrogenolysis of heavy petroleum oils orpaving asphalt, but also to hydrodesulfurization. For example, it ispossible to remove the sulfur content by about 60% from heavy oil A,heavy oil B, and paving asphalt containing sulfur in an amount of 1.9wt.%, 2.5 wt.%, and 4.8 wt.%, respectively, in the form of hydrogensulfide.

The present inventors studied to clarify the structure of the catalystconforming to this invention. Table 3 shows the results of chemicalanalysis of a catalyst, from which the experimental formula wasestimated as Mo₅ O₁₅ Na₂ H₅.

                  TABLE 3                                                         ______________________________________                                        Element     Percentage by weight (%)                                          ______________________________________                                        Mo          64.57                                                             Na          5.58                                                              H           0.06                                                              O           29.79                                                             ______________________________________                                    

FIG. 1 is a chart of differential thermal analysis of the catalyst. TheDTA curve 1 has heat absorption peaks of P1 and P2 at 515° C. and 585°C. This two-peak profile suggests either that the catalyst has twodifferent crystalline structures, or that it is made of two compounds.FIG. 2 is a chart of differential thermal analysis obtained when thecatalyst conforming to the present invention was regenerated by heattreatment. Similarly, the curve has heat absorption peaks of P3 and P4at 510° C. and 580° C. respectively. Furthermore, the curve has one moreabsorption peak of P12 at 495° C. The peaks P3 and P4 at 510° C. and580° C. show that the catalyst characteristic is not changed by heattreatment. A similar chart was obtained after the heat treatment wasrepeated three or four times.

FIGS. 3 and 4 are electron spectra of the catalyst by ESCA (electronspectroscopy for chemical analysis). The electron spectrum in FIG. 3revealed absorption peaks P5, P6, and P7 of electron on orbit 1s ofoxygen, electron on orbit 3d of molybdenum, and electron of sodium,respectively. That is, a constituent elements of the catalyst, oxygen,molybdenum and sodium were identified. Accordingly, since oxides ofmolybdenum were expected, an ESCA was measured in a coupling energyrange 227 eV to 243 eV of oxides of molybdenum. As a result, as shown inFIG. 4, an absorption peak P8 was noted at 229.3 eV. Meanwhile, thespectrum in FIG. 4 is shifted to the higher energy side by 2.3 eV. Onthe other hand, according to available literature, the coupling energyof metallic molybdenum is 226.1 eV, and that of Mo(CO)₆ and MoO₂ is226.6 eV and 230.9 eV, respectively. Therefore, the valency ofcatalyst's molybdenum was estimated to be neither 4 nor 6. The valencyof the above experimental formula Mo₅ O₁₅ Na₂ H₅ is (23/5)=4.6, whichagrees with the estimation by ESCA.

FIG. 5 is an X-ray diffraction chart of the catalyst. Absorption peaksP9, P10, and P11 were detected at rotational angles of 12.8°, 23.8°, and37.78°. The grating planes were 7.49 Å, 3.70 Å, and 2.44 Å, andsupposing the strength of 7.49 Å as 100, the strength of 3.70 Å and 2.44Å would be 33.7 and 33.7, respectively. Nothing corresponding to thisfinding is listed in ASTM, and it is known that this catalyst is a novelsubstance. The most similar matter is ASTM9-159, Mo₅ O₈ (OH)₆, of whichgrating planes are 7.33 Å, 3.68 Å, and 1.89 Å, and strengths are 90,100, and 90, respectively. In sum, these two materials are considerablydifferent from each other. In any case, since three gratings wereobserved in the X-ray diffraction, this catalyst was confirmed topossess a crystalline structure.

FIG. 6 is an infrared ray absorption spectrum of the catalyst. Acharacteristic absorption is shown at less than 900 cm⁻¹, which isestimated to be due to Mo-O or Na-O.

FIG. 7 is an infrared ray absorption spectrum of a product obtained bycausing one or more compounds selected from the group consisting ofcarbonyl compound of molybdenum, salts of molybdenum, oxides ofmolybdenum, metallic molybdenum and alloys containing molybdenum toreact with alkali and water at a temperature of 220° to 450° C. in acarbon monoxide atmosphere. Absorption is not noted at less than 900cm⁻¹. This result suggests that reduction in the presence of a phenol ata temperature of 400° to 450° C. in a hydrogen atmosphere is anindispensable process for manufacturing the catalyst conforming to thepresent invention.

The present inventors, accordingly, estimated the compositional formulaof the catalyst to be Mo₅ O₁₅ Na₂ H₅, but could not accurately determinethe constitutional formula. Supposing the compositional formula to beMo₅ O₁₅ Na₂ H₅, the chemical composition is Mo 62.25%, O 31.12%, Na5.96%, and H 0.64%, which agrees fairly well with the analytical resultin Table 3.

What is claimed is:
 1. A method for hydrogenolysis of heavy petroleumoils, which comprises contacting said oils with a catalyst in a hydrogenatmosphere having a hydrogen initial pressure of 50 kg/cm² at atemperature sufficient to effect said hydrogenolysis, said catalystbeing prepared by a process which comprises:reacting at least one memberselected from the group consisting of carbonyl compounds of molybdenum,salts of molybdenum, oxides of molybdenum, metallic molybdenum andalloys containing molybdenum, with an alkali and water at a temperaturefrom 220° to 450° C. under a carbon monoxide atmosphere, reducing theresultant reaction product in the presence of a phenol at a temperaturefrom 400° to 450° C. under a hydrogen atmosphere, and recovering saidreduced reaction product.
 2. A method according to claim 1, wherein thecarbonyl compound of molybdenum is molybdenum carbonyl.
 3. A methodaccording to claim 1, wherein the salt of molybdenum is an ammoniumsalt, nitrate, chloride, carbonate or organic acid salt of molybdenum.4. A method according to claim 1, wherein the oxide of molybdenum ismolybdenum trioxide.
 5. A method according to claim 1, wherein the alloycontaining molybdenum contains at least 0.3 weight percent ofmolybdenum.
 6. A method according to claim 1, wherein the alkali is acarbonate or phosphate of an alkali metal, a hydroxide of an alkalimetal of alkaline earth metal, or ammonium hydroxide.
 7. A methodaccording to claim 1, wherein the hydrogenolysis is conducted at atemperature of 440°-480° C.
 8. A method according to claim 1, whereinthe carbon monoxide atmosphere has an initial pressure of 100 kg/cm². 9.A method according to claim 1, wherein the hydrogen atmosphere used inpreparing the catalyst has a hydrogen initial pressure of 100 kg/cm².